WO2019094359A1 - Électrolyte de batterie à l'état solide ayant une stabilité accrue vis-à-vis de matériaux de cathode - Google Patents

Électrolyte de batterie à l'état solide ayant une stabilité accrue vis-à-vis de matériaux de cathode Download PDF

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WO2019094359A1
WO2019094359A1 PCT/US2018/059358 US2018059358W WO2019094359A1 WO 2019094359 A1 WO2019094359 A1 WO 2019094359A1 US 2018059358 W US2018059358 W US 2018059358W WO 2019094359 A1 WO2019094359 A1 WO 2019094359A1
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Prior art keywords
lithium
crystal structure
dopant
solid
electrode
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PCT/US2018/059358
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English (en)
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Jeffrey Sakamoto
Travis Thompson
Nathan Taylor
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The Regents Of The University Of Michigan
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Application filed by The Regents Of The University Of Michigan filed Critical The Regents Of The University Of Michigan
Priority to US16/761,592 priority Critical patent/US20200280093A1/en
Priority to EP18875833.8A priority patent/EP3707770A4/fr
Priority to KR1020207015590A priority patent/KR20200084008A/ko
Priority to CN201880082617.9A priority patent/CN111868994A/zh
Publication of WO2019094359A1 publication Critical patent/WO2019094359A1/fr

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    • H—ELECTRICITY
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Definitions

  • This invention relates to electrochemical devices, such as lithium ion battery electrodes, and solid-state lithium ion batteries including these electrodes and solid-state electrolytes.
  • This invention also relates to methods for making such electrochemical devices.
  • the invention relates to a composite electrode for a solid state electrochemical device wherein the electrode provides electronic and ionic conduction pathways in the electrode active material phase.
  • Lithium ion (Li-ion) battery technology has advanced significantly and has a market size projected to be $10.5 billion by 2019.
  • Current state of the art lithium ion batteries comprise two electrodes (an anode and a cathode), a separator material that keeps the electrodes from touching but allows Li + ions through, and an electrolyte (which is an organic liquid with lithium salts). During charge and discharge, Li + ions are exchanged between the electrodes.
  • SOA Li-ion technology is currently used in low volume production plug-in hybrid and niche high performance vehicles; however, widespread adoption of electrified powertrains requires 25% lower cost, four times higher performance, and safer batteries without the possibility of fire. Thus, future energy storage demands safer, cheaper and higher performance means of energy storage.
  • SOA Li-ion batteries is not compatible with advanced battery concepts, such as the use of a lithium metal anode or high voltage cathodes.
  • the liquid utilized in SOA Li-ion batteries is flammable and susceptible to combustion upon thermal runaway.
  • a cast cathode electrode may comprise cathode particles, polymeric binder (typically polyvinylidene difluoride), and conductive additive (typically acetylene black). Electron transport occurs between the cathode particles by way of the conductive additive, and the cathode particles are wet by the liquid electrolyte that provides an ionic pathway for Li + ions to transport into the cathode particles.
  • this cathode structure can be replaced with a composite cathode comprising a lithium ion conducting solid electrolyte for Li + transport, an oxide cathode active material phase, and an electronically conductive phase.
  • the solid state composite cathode provides significant transport allowing for facile movement of ions and electrons to the cathode active material phase.
  • Some solid-state cathode research has focused on replacing the current SOA Li-ion cathode, which has a liquid electrolyte that provides facile transport of Li ions to individual cathode particles.
  • Thin film type LiPON (nitrogen doped lithium phosphate) batteries have been successfully produced with ⁇ 10 micron cathode layers but at low areal loading.
  • cathode layers must be up to 100 microns in thickness.
  • cathodes such as the layered type (e.g., lithium cobalt oxide - L1C0O2 - LCO, and lithium nickel cobalt manganese oxide - LiNiCoMn02 - NMC), olivine, or spinel, lack sufficient ionic and electronic conductivities to enable cathodes of this thickness.
  • areal capacities of 1 .0-5.0 mAh/cm 2 can only be achieved in all solid-state batteries with a composite system in which there are one or more discrete phases conducting Li ions and electrons in addition to the cathode phase.
  • the electrode may be a cathode or an anode.
  • the electrode comprises a lithium host material having a structure (which may be porous); and a solid-state conductive electrolyte material of the present disclosure filling at least part (or all) of the structure.
  • the invention provides an electrode for an electrochemical device.
  • the electrode comprises a lithium host material; and a solid-state conductive material comprising a ceramic material having a crystal structure and a dopant in the crystal structure, wherein the solid-state conductive material retains the crystal structure during sintering with the lithium host material.
  • the crystal structure having the dopant has a higher fraction of a cubic structure after sintering relative to the crystal structure having no dopant.
  • the crystal structure having the dopant has a lower fraction of a tetragonal structure after sintering relative to the crystal structure having no dopant.
  • the dopant may be a transition metal cation.
  • the dopant may be pentavalent or hexavalent.
  • the dopant may comprise tantalum.
  • the dopant may comprise niobium.
  • the dopant can be present in the crystal structure at 1 to 20 weight percent based on a total weight of chemical elements in the crystal structure.
  • the solid-state conductive material has a lithium ion
  • the solid-state conductive material has a lithium ion conductivity that is greater than 10 "4 S/cm at 23°C.
  • the solid-state conductive material can have a formula of LiwAxl hRes-yOz wherein w is 5 - 7.5,
  • A is selected from B, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, Co, Fe, and any combination thereof,
  • M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof,
  • Re is selected from lanthanide elements, actinide elements, and any combination thereof
  • M is a combination of Zr and Ta (e.g. , doping of a Li7La3Zr20i2 structure on the Zr site with Ta, such as Li6.5La3Zn.5Tao.5O12).
  • M is a combination of Zr and Nb (e.g. , doping of a Li7La3Zr2Oi2 structure on the Zr site with Nb).
  • the electrode may be a cathode for the electrochemical device, and the lithium host material may be selected from the group consisting of lithium metal oxides wherein the metal is one or more aluminum, cobalt, iron, manganese, nickel and vanadium, and lithium-containing phosphates having a general formula LiMPO4 wherein M is one or more of cobalt, iron, manganese, and nickel.
  • the lithium host material may be selected from UC0O2, LiNiO2, Li(NiCoAI)i.o02, Li(MnNi) 2 .oO4, LiFePO4,
  • the electrode may be an anode for the electrochemical device, and the lithium host material may be selected from the group consisting of graphite, lithium titanium oxides, hard carbon, tin and cobalt alloy, or silicon and carbon.
  • the electrode may further comprise a conductive additive.
  • the conductive additive may be selected from graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, conductive fibers, metallic powders, conductive whiskers, conductive metal oxides, and mixtures thereof.
  • the invention provides a method for forming an electrode for an electrochemical device.
  • the method comprises the steps of: (a) forming a mixture comprising (i) a lithium host material, and (ii) a solid-state conductive material comprising a ceramic material having a crystal structure and a dopant in the crystal structure; and (b) sintering the mixture, wherein the dopant is selected such that the solid-state conductive material retains the crystal structure during sintering with the lithium host material.
  • step (a) can comprise casting a slurry including the mixture on a surface to form a layer, and step (b) comprises sintering the layer.
  • step (b) can further comprise sintering the mixture at a temperature between 20°C and 1400°C.
  • step (b) can further comprise sintering the mixture between 1 minute and 48 hours.
  • step (b) can comprise sintering the mixture at a temperature in a range of 600°C to 1 100°C.
  • the dopant may be pentavalent or hexavalent.
  • the dopant can be tantalum.
  • the dopant can be niobium.
  • the dopant can be present in the crystal structure at 1 to 20 weight percent based on a total weight of chemical elements in the crystal structure.
  • the solid-state conductive material can have a formula of
  • A is selected from B, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, Co, Fe, and any combination thereof,
  • M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof,
  • Re is selected from lanthanide elements, actinide elements, and any combination thereof, wherein y is 0.01 - 0.75,
  • M is a combination of Zr and Ta (e.g. , doping of a Li7La3Zr20i2 structure on the Zr site with Ta, such as Li6.5La3Zn.5Tao.5O12).
  • M is a combination of Zr and Nb (e.g. , doping of a Li7La3Zr2Oi2 structure on the Zr site with Nb).
  • the electrode may be a cathode for the electrochemical device
  • the lithium host material may be selected from the group consisting of lithium metal oxides wherein the metal is one or more aluminum, cobalt, iron, manganese, nickel and vanadium, and lithium-containing phosphates having a general formula LiMPO4 wherein M is one or more of cobalt, iron, manganese, and nickel.
  • the lithium host material may be selected from L1C0O2, LiNiO2, Li(NiCoAI)i.oO2, Li(MnNi)2.oO4, LiFePO4, L1C0PO4, LiNiPo4, or L1VO3, and any combination thereof.
  • the electrode may be an anode for the electrochemical device
  • the lithium host material may be selected from the group consisting of graphite, lithium titanium oxides, hard carbon, tin and cobalt alloy, or silicon and carbon.
  • the electrode may further comprise a conductive additive.
  • the conductive additive may be selected from graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, conductive fibers, metallic powders, conductive whiskers, conductive metal oxides, and mixtures thereof.
  • the invention provides an electrochemical device, such as a lithium ion battery or a lithium metal battery.
  • the electrochemical device comprises a cathode, an anode, and a solid-state electrolyte configured to facilitate the transfer of lithium ions between the anode and the cathode.
  • the cathode can comprise a lithium host material having a first structure (which may be porous).
  • the anode can comprise a lithium metal, or a lithium host material having a second structure (which may be porous).
  • a solid-state conductive material of the present disclosure fills at least part (or all) of the first structure in the lithium host material of the cathode and/or a second structure of the lithium host material of the anode (in the case of a lithium ion battery).
  • the solid-state conductive material comprises a ceramic material having a crystal structure and a dopant in the crystal structure; and the dopant is selected such that the solid-state conductive material retains the crystal structure during sintering with the lithium host material.
  • the crystal structure having the dopant can have a higher fraction of a cubic structure after sintering relative to the crystal structure having no dopant.
  • the crystal structure having the dopant can have a lower fraction of a tetragonal structure after sintering relative to the crystal structure having no dopant.
  • the dopant may be a transition metal cation.
  • the dopant may be pentavalent or hexavalent.
  • the dopant may be tantalum.
  • the dopant may be niobium.
  • the dopant can be present in the crystal structure at 1 to 20 weight percent based on a total weight of chemical elements in the crystal structure.
  • the solid-state conductive material can have a lithium ion conductivity that is greater than 10 5 S/cm at 23°C.
  • the solid-state conductive material can have a lithium ion conductivity that is greater than 10 ⁇ 4 S/cm at 23°C.
  • the solid-state conductive material may have a formula of LiwAxl hRes-yOz
  • A is selected from B, Ga, In, Zn, Cd, Y, Sc, Mg, Ca, Sr, Ba, Co, Fe, and any combination thereof,
  • M is selected from Zr, Hf, Nb, Ta, Mo, W, Sn, Ge, Si, Sb, Se, Te, and any combination thereof, wherein Re is selected from lanthanide elements, actinide elements, and any combination thereof,
  • M is a combination of Zr and Ta (e.g. , doping of a Li7La3Zr20i2 structure on the Zr site with Ta, such as Li6.5La3Zn.5Tao.5O12).
  • M is a combination of Zr and Nb (e.g. , doping of a Li7La3Zr2Oi2 structure on the Zr site with Nb).
  • the cathode can comprise the lithium host material and the solid-state conductive material
  • the lithium host material may be selected from the group consisting of lithium metal oxides wherein the metal is one or more aluminum, cobalt, iron, manganese, nickel and vanadium, and lithium- containing phosphates having a general formula LiMPO4 wherein M is one or more of cobalt, iron, manganese, and nickel.
  • the cathode can comprise the lithium host material and the solid-state conductive material, and the lithium host material may be selected from UC0O2, LiNiO2, Li(NiCoAI)i.oO2, Li(MnNi) 2 .oO4, LiFePO4, UC0PO4, LiNiPo4, or L1VO3, and any combination thereof.
  • the anode can comprise the lithium host material and the solid-state conductive material, and the lithium host material may be selected from the group consisting of graphite, lithium titanium oxides, hard carbon, tin and cobalt alloy, or silicon and carbon.
  • LLZO is one of the most attractive solid electrolytes for all solid-state batteries.
  • AI: LLZO (LLZO doped with aluminum to stabilize the cubic crystal structure at room temperature) is attractive due to low cost, high ionic conductivity, and stability towards metallic lithium.
  • LLZO LLZO doped with aluminum to stabilize the cubic crystal structure at room temperature
  • a mixture of cathode particles, electrolyte particles, and optionally conductive additive particles must be co-sintered at temperatures of 20°C to 1400°C for densification.
  • Our work on composite cathodes has revealed a distinct mechanism whereby AI:LLZO reacts during co-sintering with common cathode materials, such as lithium cobalt oxide (LCO) and lithium nickel cobalt manganese oxide (NMC).
  • LCO lithium cobalt oxide
  • NMC lithium nickel cobalt manganese oxide
  • the invention improves the composite electrode through chemical modification of a lithium-ion conducting solid electrolyte material which maintains significant ionic conductivity after co-sintering with a lithium host material.
  • Doping of the Li7La3Zr2Oi2 structure on the Zr site with a transition metal cation preferably pentavalent or hexavalent maintains significant ionic conduction after co-sintering with the lithium host material.
  • Doping of the Li7La3Zr2Oi2 structure with other transition metal cations (such as cobalt) can also provide electronic conduction.
  • the resulting solid state composite electrode can operate as a mixed ionic / electronic conductor, eliminating the need for a separate phase that provides an electrical pathway from the current collector to electrode active material particles.
  • Figure 1 is a schematic of a lithium ion battery.
  • Figure 2 is a schematic of a lithium metal battery.
  • Figure 3 shows AI:LLZO (LLZO doped with aluminum) before (bottom) and after (top) co-sintering with a lithium nickel cobalt manganese oxide (NMC) cathode at 700°C for 30 minutes.
  • NMC lithium nickel cobalt manganese oxide
  • Figure 4 shows Ta:LLZO (LLZO doped with tantalum) before (bottom) and after (top) co-sintering with lithium nickel cobalt manganese oxide (NMC) at 900°C for 30 minutes.
  • NMC lithium nickel cobalt manganese oxide
  • an electrode according to embodiments of the invention can be used in a lithium ion battery as depicted in Figure 1 .
  • the lithium ion battery 1 0 of Figure 1 includes a current collector 12 (e.g., aluminum) in contact with a cathode 14.
  • a solid state electrolyte 16 is arranged between the cathode 14 and an anode 1 8, which is in contact with a current collector 22 (e.g., aluminum).
  • the current collectors 12 and 22 of the lithium ion battery 1 0 may be in electrical communication with an electrical component 24.
  • the electrical component 24 could place the lithium ion battery 1 0 in electrical communication with an electrical load that discharges the battery or a charger that charges the battery.
  • a suitable active material for the cathode 14 of the lithium ion battery 10 is a lithium host material capable of storing and subsequently releasing lithium ions.
  • An example cathode active material is a lithium metal oxide wherein the metal is one or more of aluminum, cobalt, iron, manganese, nickel and vanadium.
  • Non-limiting example lithium metal oxides are LiCoO2 (LCO), LiFeO2, LiMnO2 (LMO), LiMn2O4,
  • LiNiCoMnO2 (NMC), UN1O2 (LNO), LiNi x Co y O2, LiMn x Co y O2, LiMn x Ni y O2, LiMn x Ni y O4, LiNi x Co y AlzO2, LiNii 3Mm 3Coi 3O2 and others.
  • Another example of cathode active materials is a lithium-containing phosphate having a general formula L1MPO4 wherein M is one or more of cobalt, iron, manganese, and nickel, such as lithium iron phosphate (LFP) and lithium iron fluorophosphates.
  • the cathode active material can be a mixture of any number of these cathode active materials.
  • the lithium host material is selected from the group consisting of lithium metal oxides wherein the metal is one or more aluminum, cobalt, iron, manganese, nickel and vanadium, and lithium-containing phosphates having a general formula LiMP04 wherein M is one or more of cobalt, iron, manganese, and nickel.
  • the lithium host material is selected from L1C0O2, LiNi02, Li(NiCoAI)i.o02, Li(MnNi) 2 .o04, LiFeP04, UC0PO4, LiNiPo4, or L1VO3, and any combination thereof.
  • the cathode 14 may include a conductive additive.
  • a conductive additive e.g., Co, Mn, Ni, Cr, Al, or Li
  • conductive additives e.g., Co, Mn, Ni, Cr, Al, or Li
  • Other suitable conductive additives include graphite, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, conductive fibers, metallic powders, conductive whiskers, conductive metal oxides, and mixtures thereof.
  • a suitable active material for the anode 18 of the lithium ion battery 10 is a lithium host material capable of incorporating and subsequently releasing the lithium ion such as graphite, a lithium metal oxide (e.g., lithium titanium oxide), hard carbon, a tin/cobalt alloy, tin/aluminum alloy, or silicon/carbon.
  • the anode active material can be a mixture of any number of these anode active materials.
  • the anode 18 may include one or more of the conductive additives described above.
  • a suitable solid state electrolyte 16 of the lithium ion battery 10 includes an electrolyte material having the formula LiuRevMwAxOy, wherein
  • Re can be any combination of elements with a nominal valance of +3 including
  • M can be any combination of metals with a nominal valance of +3, +4, +5 or +6 including Zr, Ta, Nb, Sb, W, Hf, Sn, Ti, V, Bi, Ge, and Si;
  • A can be any combination of dopant atoms with nominal valance of +1 , +2, +3 or +4 including H, Na, K, Rb, Cs, Ba, Sr, Ca, Mg, Fe, Co, Ni, Cu, Zn, Ga, Al, B, and Mn; u can vary from 3 - 7.5;
  • v can vary from 0 - 3;
  • w can vary from 0 - 2;
  • x is 0-2;
  • y can vary from 1 1 - 12.5.
  • an electrode according to embodiments of the invention can be used in a lithium metal battery as depicted in Figure 2.
  • the lithium metal battery 1 10 of Figure 2 includes a current collector 1 12 in contact with a cathode 1 14.
  • a solid state electrolyte 1 16 is arranged between the cathode 1 14 and an anode 1 18, which is in contact with a current collector 122.
  • the current collectors 1 12 and 122 of the lithium metal battery 1 10 may be in electrical communication with an electrical component 124.
  • the electrical component 124 could place the lithium metal battery 1 10 in electrical communication with an electrical load that discharges the battery or a charger that charges the battery.
  • a suitable active material for the cathode 1 14 of the lithium metal battery 1 10 is one or more of the lithium host materials listed above, or porous carbon (for a lithium air battery), or a sulfur containing material (for a lithium sulfur battery).
  • the cathode 1 14 may include one or more of the conductive additives described above.
  • a suitable active material for the anode 1 18 of the lithium metal battery 1 10 is lithium metal.
  • a suitable solid state electrolyte material for the solid state electrolyte 1 16 of the lithium metal battery 1 10 is one or more of the solid state electrolyte materials listed above.
  • the present invention provides embodiments of an electrode that provide improved electronic and ionic conduction pathways in the electrode active material phase (e.g., lithium host material) of a cathode or an anode suitable for use in the lithium ion battery 10 of Figure 1 or the lithium metal battery 1 10 of Figure 2.
  • the electrode active material phase e.g., lithium host material
  • Transition metal (e.g., Ta, Nb) doped LLZO can be produced by direct solid state reaction of transition metal oxides or a transition metal and LLZO during synthesis.
  • one or more additional transition metal cations (such as cobalt) can be diffused into the LLZO at a temperature (e.g., 600-1000°C) from a transition metal or transition metal oxide species in the gas phase.
  • tantalum and niobium are used as examples, it is expected that other dopants including transition metal cations, preferably pentavalent or hexavalent, can similarly prevent the conversion of cubic LLZO to tetragonal LLZO during co-sintering of LLZO with lithium host materials.
  • the invention provides a composite electrode for an electrochemical device.
  • the electrode may be a cathode or an anode.
  • the electrode comprises a lithium host material having a structure (which may be porous); and a solid-state conductive material comprising a ceramic material having a crystal structure and a dopant in the crystal structure.
  • the dopant is selected such that the solid-state conductive material retains the crystal structure during sintering with the lithium host material.
  • one non-limiting example solid-state conductive material is Li6.5La3Zn.5Tao.5O12, in which the dopant level of tantalum is 12.5 wt.% Ta2Os or 10.3 wt.% Ta elemental.
  • the dopant may be present in the crystal structure of the solid-state conductive material at 0.05 to 20 weight percent based on a total weight of the chemical elements in the crystal structure, or the dopant may be present in the crystal structure at greater than 0.01 weight percent based on a total weight of the chemical elements in the crystal structure, or the dopant may be present in the crystal structure at 1 to 20 weight percent based on a total weight of the chemical elements in the crystal structure, or the dopant may be present in the crystal structure at 5 to 15 weight percent based on a total weight of the chemical elements in the crystal structure.
  • transition metal doping of garnet LLZO phase can ensure that ionic conductivity is minimally changed. Tantalum and niobium, in particular, readily dope the LLZO structure.
  • the transition metal cation dopant e.g., tantalum and niobium
  • the transition metal cation dopant may be from any appropriate transition metal containing source.
  • the invention provides an electrochemical device, such as the lithium ion battery 10 of Figure 1 or the lithium metal battery 1 10 of Figure 2.
  • the electrochemical device comprises a cathode, an anode, and a solid-state electrolyte configured to facilitate the transfer of ions between the anode and the cathode.
  • the cathode can comprise a lithium host material having a first structure (which may be porous).
  • the anode can comprise a lithium metal, or a lithium host material having a second structure (which may be porous).
  • a solid-state conductive material comprising a ceramic material having a crystal structure and a dopant in the crystal structure fills at least part (or all) of the first structure in the lithium host material of the cathode and/or a second structure of the lithium host material of the anode (in the case of a lithium ion battery).
  • the lithium host materials are sintered.
  • the dopant is selected such that the solid-state conductive material retains the crystal structure during sintering with the lithium host material.
  • the solid-state conductive material has lithium ion conductivity that is greater than 10 -5 S/cm at 23 degrees Celsius, or that is greater than 10 "4 S/cm at 23 degrees Celsius.
  • the invention provides a method for forming a composite electrode for an electrochemical device.
  • the method comprises: (a) forming a mixture comprising (i) a lithium host material, and (ii) a solid-state conductive material comprising a ceramic material having a crystal structure and a dopant in the crystal structure; and (b) sintering the mixture, wherein the dopant is selected such that the solid-state conductive material retains the crystal structure during sintering with the lithium host material.
  • the mixture may be sintered at a temperature between 20 and 1400°C for a time period between 1 minute and 48 hours, or between 1 minute and 1 hour.
  • the method may comprise casting a slurry including the mixture on a surface to form a layer, and step (b) may comprise sintering the layer.
  • the slurry to be cast may include optional components.
  • the slurry may optionally include one or more sintering aids which melt and form a liquid that can assist in sintering of a cast slurry formulation of the invention via liquid phase sintering.
  • Example sintering aids can be selected from boric acid, boric acid salts, boric acid esters, boron alkoxides phosphoric acid, phosphoric acid salts, phosphate acid esters, silicic acid, silicic acid salts, silanols, silicon alkoxides, aluminum alkoxides and mixtures thereof.
  • the slurry may optionally include a dispersant.
  • a dispersant One purpose of the dispersant is to stabilize the slurry and prevent the suspended active battery material particles from settling out.
  • the dispersant may be selected from the group consisting of salts of lithium and a fatty acid.
  • the fatty acid may be selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, and behenic acid.
  • the slurry may optionally include a plasticizer.
  • the purpose of the plasticizer is to increase the workability of the as-cast tape.
  • the plasticizer is a naturally derived plant based oil.
  • the plasticizer may be selected from the group consisting of coconut oil, castor oil, soybean oil, palm kernel oil, almond oil, corn oil, canola oil, rapeseed oil, and mixtures thereof.
  • the slurry formulation may optionally include a binder.
  • a binder include: poly(methylmethacrylate), poly(vinylacetate), polyvinyl alcohol, polyethyleneoxide, polyvinylpyrrolidone, polyvinyl ether,
  • polyvinylchloride polyacrylonitrile, polyvinylpyridine, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polyethylene, polypropylene, ethylene-propylene-diene terpolymers (EPDM), cellulose, carboxymethylcellulose, starch,
  • the binder is preferably a non- fluorinated polymeric material.
  • the slurry may optionally include a solvent is useful in a slurry formulation to dissolve the binder and act as a medium for mixing the other additives. Any suitable solvents may be used for mixing the active battery material particles, dispersant, and binder into a uniform slurry.
  • Suitable solvents may include alkanols (e.g., ethanol), nitriles (e.g., acetonitrile), alkyl carbonates, alkylene carbonates (e.g., propylene carbonate), alkyl acetates, sulfoxides, glycol ethers, ethers, N-methyl-2- pyrrolidone, dimethylformamide, dimethylacetamide, tetrahydrofuran, or a mixture of any of these solvents.
  • alkanols e.g., ethanol
  • nitriles e.g., acetonitrile
  • alkyl carbonates e.g., propylene carbonate
  • alkyl acetates e.g., sulfoxides
  • glycol ethers, ethers, N-methyl-2- pyrrolidone dimethylformamide
  • dimethylacetamide dimethylacetamide
  • tetrahydrofuran or a mixture of
  • the slurry formulation may include other additives.
  • the cathode or anode active battery material particles may be mixed with other particles, such as conductive particles.
  • Any conductive material may be used without particular limitation so long as it has suitable conductivity without causing chemical changes in the fabricated battery. Examples of conductive materials include graphite; carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; conductive fibers such as carbon fibers and metallic fibers; metallic powders such as aluminum powder and nickel powder;
  • conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives.
  • Any suitable method may be used to mix the slurry components into a uniform slurry. Suitable mixing methods may include sonication, mechanical stirring, physical shaking, vortexing, ball milling, and any other suitable means.
  • the formulation is cast on a substrate surface to form a cast tape layer.
  • the substrate may include any stable and conductive metals suitable as a current collector for the battery.
  • a suitable metallic substrate may include aluminum, copper, silver, iron, gold, nickel, cobalt, titanium, molybdenum, steel, zirconium, tantalum, and stainless steel.
  • the metal substrate is aluminum.
  • the slurry layer cast on the surface may have a thickness in the range of a few micrometers to a few centimeters.
  • the thickness of the cast slurry layer is in the range of 10 micrometers to 150 micrometers, preferably 10 micrometers to 100 micrometers.
  • the green tape can be dried and sintered to a composite electrode having a thickness in the range of 10 micrometers to 150 micrometers, preferably 20 micrometers to 100 micrometers, more preferably 50 micrometers to 100
  • the anode can be cast first on the metal substrate, followed by casting the solid electrolyte on the anode, and finally casting the cathode on the electrolyte.
  • the cathode can be cast first on the metal substrate, followed by the solid electrolyte, and finally the anode.
  • the multi-layer green tape can be dried and sintered at a temperature in a range of 600°C to 1 100°C, or in a range of 800°C to 1000°C, to achieve the necessary electrochemical properties.
  • Figure 3 gives a plot of an XRD pattern for AI:LLZO before and after co- sintering with lithium nickel cobalt manganese oxide (NMC) at 700°C.
  • the AI:LLZO was present at 51 % by weight in the NMC.
  • the (1 12) peak intensity increases with respect to the (21 1 ) peak after co-sintering, indicating increased tetragonal LLZO fraction.
  • Figure 4 gives XRD patterns for Ta:LLZO sintered with lithium nickel cobalt manganese oxide (NMC) to 900°C.
  • the Ta:LLZO was present at 51 % by weight in the NMC.
  • the invention provides electrochemical devices, such as lithium ion battery composite electrodes, and solid-state lithium ion batteries including these composite electrodes and solid-state electrolytes.
  • the composite electrodes include one or more separate phases within the electrode that provide electronic and ionic conduction pathways in the electrode active material phase.
  • the solid state electrochemical devices have applications in electric vehicles, consumer electronics, medical devices, oil/gas, military, and aerospace.

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Abstract

L'invention concerne des dispositifs électrochimiques, tels que des électrodes de batterie au lithium-ion, des électrolytes à l'état solide à conduction d'ions lithium, et des batteries au lithium-ion à l'état solide comprenant ces électrodes et électrolytes à l'état solide. L'invention concerne en outre des électrodes composites pour dispositifs électrochimiques à l'état solide. Les électrodes composites comprennent une ou plusieurs phases distinctes à l'intérieur de l'électrode, qui fournissent des voies de conduction électronique et ionique dans la phase de matériau actif d'électrode. L'invention concerne également un procédé de formation d'une électrode composite pour un dispositif électrochimique. Un exemple de procédé comprend (a) la formation d'un mélange comprenant (i) un matériau hôte au lithium, et (ii) un matériau conducteur à l'état solide comprenant un matériau céramique ayant une structure cristalline et un dopant dans la structure cristalline ; et (b) le frittage du mélange, le dopant étant choisi de sorte que le matériau conducteur à l'état solide retient la structure cristalline pendant le frittage avec le matériau hôte au lithium.
PCT/US2018/059358 2017-11-07 2018-11-06 Électrolyte de batterie à l'état solide ayant une stabilité accrue vis-à-vis de matériaux de cathode WO2019094359A1 (fr)

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US16/761,592 US20200280093A1 (en) 2017-11-07 2018-11-06 Solid-State Battery Electrolyte Having Increased Stability Towards Cathode Materials
EP18875833.8A EP3707770A4 (fr) 2017-11-07 2018-11-06 Électrolyte de batterie à l'état solide ayant une stabilité accrue vis-à-vis de matériaux de cathode
KR1020207015590A KR20200084008A (ko) 2017-11-07 2018-11-06 캐소드 물질에 대한 안정성이 증가된 고체-상태 배터리 전해질
CN201880082617.9A CN111868994A (zh) 2017-11-07 2018-11-06 对于阴极材料具有提高稳定性的固态电池电解质

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CN111868994A (zh) 2020-10-30
EP3707770A4 (fr) 2021-09-01

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